Functional solution supply system

ABSTRACT

A sulfuric acid electrolyte is produced efficiently as a functional solution and persulfuric acid produced by electrolysis is supplied efficiently to a use side while suppressing self-decomposition thereof. 
     A functional solution supply system adapted to electrolyze a sulfuric acid solution to prepare a functional solution and supply the functional solution to a use side, comprises a storage tank  2  for storing the sulfuric acid solution, an electrolyzing apparatus (electrolytic cell  3 ) for electrolyzing the sulfuric acid solution, heating means (heater  5 ) for heating the sulfuric acid solution, cooling means (cooler  4 ) for cooling the sulfuric acid solution, a first circulation line  11  for returning the sulfuric acid solution discharged from the storage tank  2  to the storage tank  2  through the electrolyzing apparatus without passing through the heating means, a second circulation line  12  for returning the sulfuric acid solution introduced from the use side (cleaning machine  1 ) to the use side through the cooling means and the storage tank  2  in this order without passing through the heating means, and a third circulation line  13  for returning the sulfuric acid solution introduced from the use side to the use side through the heating means (heater  5 ) without passing through the cooling means and the storage tank  2.

TECHNICAL FIELD

The present invention relates to a functional solution supply systemcapable of supplying a functional solution containing persulfuric acid,for example, as a cleaning solution.

BACKGROUND ART

A one loop type shown in FIG. 2( a) is known as a simplest systemconfiguration of a semiconductor wafer resist stripping system whichuses a persulfuric acid solution prepared by the electrolysis of asulfuric acid solution.

In this system, an liquid outlet side of a cleaning machine 21 and anliquid inlet side of an electrolytic cell 23 are connected together by afeed line of a circulation line 31 through a cooler 24 and a storagetank 22, and an liquid outlet side of the electrolytic cell 23 and anliquid inlet side of the cleaning machine 21 are connected together by areturn line of the circulation line 31 through a heater 25. Thus, thecomponents are connected together in one loop.

This system has advantage of a reduced number of pumps and valves, butinvolves the following problems.

In the case where the amount of persulfuric acid required per unit timein the cleaning machine is large, that is, in the case where the iondose for a semiconductor wafer is large or the resist thickness is largeor the processing time is to be shortened, it is necessary to install alarge number of electrolytic cells in order to produce a persulfuricacid solution of a high concentration. However, an increase in theamount of a sulfuric acid solution circulated leads to an increase of acooling load on the cooler and an increase of a reheating load on theheater. If the amount of the sulfuric acid solution circulated is small,it is impossible to maintain a proper flow rate distribution of thesulfuric acid solution in the interior of the electrolytic cell.

These problems may be solved by adopting a two loops type shown in FIGS.2( b) and 2(c) or a three loops type shown in FIG. 2( d). (See, forexample, FIG. 2 in Patent Document 1.)

In the system of FIG. 2( b), a cleaning machine 21 and a storage tank 22are connected together by a feed line of a circulation line 31 a, andthe storage tank 22 and the cleaning machine 21 are connected togetherby a return line of the circulation line 31 a through a heater 25.Further, the storage tank 22 and an electrolytic cell 23 are connectedtogether by a feed line of a circulation line 31 b through a cooler 26,and the electrolytic cell 23 and the storage tank 22 are connectedtogether by a return line of the circulation line 31 b. A heater 27 isinstalled in the storage tank 22 to prevent a drop in temperature of acirculating solution. That is, the components are connected together intwo loops, one of which is formed by the feed line of the circulationline 31 a and the return line of the circulation line 31 a and the otherof which is formed by the feed line of the circulation line 31 b and thereturn line of the circulation line 31 b.

In the system of FIG. 2( c), a cleaning machine 21 and a storage tank 22are connected together by a feed line of a circulation line 31 a, andthe storage tank 22 and the cleaning machine 21 are connected togetherby a return line of the circulation line 31 a through a heater 25.Further, the storage tank 22 and an electrolytic cell 23 are connectedtogether by a circulation line 31 b through a cooler 26, and theelectrolytic cell 23 and the cleaning machine 21 are connected togetherby a circulation line 31. A heater 27 is installed in the storage tank22 to prevent a drop in temperature of a circulating solution. That is,the components are connected together in two loops, one of which isformed by the feed line of the circulation line 31 a and the return lineof the circulation line 31 a and the other of which is formed by thefeed line of the circulation line 31 a, the circulation line 31 b andthe circulation line 31.

In the system of FIG. 2( d), a cleaning machine 21 and a storage tank 22are connected together by a feed line of a circulation line 31 a, andthe storage tank 22 and the cleaning machine 21 are connected togetherby a return line of the circulation line 31 a through a heater 25.Further, the storage tank 22 and an electrolytic cell 23 are connectedtogether by a feed line of a circulation line 31 b through a cooler 26,and the electrolytic cell 23 and the storage tank 22 are connectedtogether by a return line of the circulation line 31 b. Further, theelectrolytic cell 23 and the cleaning machine 21 are connected togetherby a circulation line 31. A heater 27 is installed in the storage tank22 to prevent a drop in temperature of a circulating solution. That is,the components are connected together in three loops, which are the loopformed by the feed line of the circulation line 31 a and the return lineof the circulation line 31 a, the loop formed by the feed line of thecirculation line 31 b and the return line of the circulation line 31 b,and the loop formed by the feed line of the circulation line 31 a, thefeed line of the circulation line 31 b and the circulation line 31.

Thus, in the conventional art, the storage tank was used as a reactionsite for expediting a resist decomposing reaction secondarily.

-   Patent Document 1: Japanese Patent Laid-Open No. 2007-266495

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

In the system of FIG. 2( b), a persulfuric acid solution produced in theelectrolytic cell 23 is added, in the storage tank 22, to thecirculating solution which contains residual resist discharged from thecleaning machine 21. Therefore, the resist can be decomposed positivelyin the storage tank 22. Besides, since the adjustment of a flow rate inthe loop circulating from the storage tank 22 through the electrolyticcell 23 can be done substantially independently of a flow rate in theloop circulating from the cleaning machine 21 through the storage tank22, a proper flow rate distribution of the sulfuric acid solution can bemaintained in the interior of the electrolytic cell 23 irrespective ofan increase or decrease in the amount of the sulfuric acid solutioncirculating to the cleaning machine 21.

However, since the total amount of the circulating solution from thecleaning machine 21 is circulated through the storage tank 22, it isnecessary to install the heater 27 separately in the storage tank 22 inorder to decrease the load on the heater 25 at the time of feeding thestored solution of a lowered temperature from the storage tank 22 backto the cleaning machine 21. With the heater 27, the sulfuric acidsolution in the storage tank 22 is held at a high temperature, so thatthe persulfuric acid flowing into the storage tank 22 decomposes byitself immediately, thus giving rise to the problem that it is difficultto supply a highly concentrated persulfuric acid solution to thecleaning machine 21.

In the system of FIG. 2( c), since the adjustment of a flow rate in theloop circulating from the cleaning machine 21 through both storage tank22 and electrolytic cell 23 can be done substantially independently of aflow rate in the loop circulating from the cleaning machine 21 throughthe storage tank 22, a proper flow rate distribution of the sulfuricacid solution can be maintained in the interior of the electrolytic cell23 irrespective of an increase or decrease in the amount of the sulfuricacid solution circulating to the cleaning machine 21. Besides, since thecooled sulfuric acid solution is electrolyzed, a persulfuric acidsolution can be produced with high efficiency of electrolysis. Moreover,since the persulfuric acid solution is not heated in the circulationline 31, it can be supplied to the cleaning machine 21 before progressof the self-decomposition.

However, there is a problem that in the case where the amount ofpersufuric acid required per unit time in the cleaning machine 21 islarge, that is, in the case where the ion dose for a semiconductor waferis large or the resist thickness is large or the processing time is tobe shortened, it becomes necessary to install a large number ofelectrolytic cells 23 in order to produce a highly concentratedpersulfuric acid solution in a short time.

In the system of FIG. 2( d), since the persulfuric acid solutionproduced in the electrolytic cell 23 is added, in the storage tank 22,to the circulating solution which contains residual resist dischargedfrom the cleaning machine 21, the resist can be decomposed positively.Besides, since the adjustment of a flow rate in the loop circulatingfrom the cleaning machine 21 through both storage tank 22 and theelectrolytic cell 23 and the adjustment of flow rate in the loopcirculating from the storage tank 22 through the electrolytic cell 23can be done substantially independently of a flow rate in the loopcirculating from the cleaning machine 21 through the storage tank 22, aproper flow rate distribution of the sulfuric acid solution can bemaintained in the interior of the electrolytic cell 23 irrespective ofan increase or decrease in the amount of the sulfuric acid solutioncirculating to the cleaning machine 21. Moreover, since the cooledsulfuric acid solution is electrolyzed, a persulfuric acid solution canbe produced with high efficiency of electrolysis. Further, since thepersulfuric acid solution is not heated in the circulation line 31, itcan be supplied to the cleaning machine 21 before progress of theself-decomposition.

However, also in this case, since the total amount of the circulatingsolution from the cleaning machine 21 is circulated to the storage tank22, it is necessary to install the heater 27 separately in the storagetank 22 in order to decrease the load on the heater 25 at the time offeeding the stored solution of a lowered temperature from the storagetank 22 back to the cleaning machine 21. With the heater 27, thesulfuric acid solution in the storage tank 22 is held at a hightemperature, so that the persulfuric acid flowing into the storage tank22 decomposes by itself immediately. Thus, there still remains a problemthat it is difficult to supply a highly concentrated persulfuric acidsolution to the cleaning machine 21. Further, there still remains aproblem that in the case where the amount of persulfuric acid requiredper unit time in the cleaning machine 21 is large, that is, in the casewhere the ion dose for a semiconductor wafer is large or the resistthickness is thick or the processing time is to be shortened, it becomesnecessary to install a large number of electrolytic cells 23 in order toproduce a highly concentrated persulfuric acid solution.

The present invention has been accomplished under the abovecircumstances and it is an object of the invention to provide afunctional solution supply system capable of producing a functionalsolution of high performance while decreasing the number of electrolyticcells installed and further capable of supplying the functional solutionto a use side.

Means for Solving the Problems

That is, the functional solution supply system of a first aspect of thepresent invention is a functional solution supply system forelectrolyzing a sulfuric acid solution to prepare a functional solutionand supplying the functional solution to a use side, the systemcomprising a storage tank for storing the sulfuric acid solution, anelectrolyzing apparatus for electrolyzing the sulfuric acid solution,heating means for heating the sulfuric acid solution, cooling means forcooling the sulfuric acid solution, and the following three circulationlines:

1. a first circulation line for returning the sulfuric acid solutiondischarged from the storage tank to the storage tank through theelectrolyzing apparatus without passing through the heating means;

2. a second circulation line for returning the sulfuric acid solutionintroduced from the use side to the use side through the cooling meansand the storage tank in this order without passing through the heatingmeans; and

3. a third circulation line for returning the sulfuric acid solutionintroduced from the use side to the use side through the heating meanswithout passing through the cooling means and the storage tank.

The functional solution supply system of a second aspect of the presentinvention is characterized in that the second circulation line and thethird circulation line join just before the return to the use side inthe above first aspect.

The functional solution supply system of a third aspect of the presentinvention is characterized in that the second circulation line and thethird circulation line are branched after being introduced from the useside in the above first or second aspect.

The functional solution supply system of a fourth aspect of the presentinvention is characterized in that on a downstream side of the storagetank and on an upstream side of the electrolyzing apparatus the firstcirculation line includes second cooling means for cooling the sulfuricacid solution in any of the above first to third aspects.

The functional solution supply system of a fifth aspect of the presentinvention is characterized in that on a downstream side of theelectrolyzing apparatus and on an upstream side of the storage tank thefirst circulation line includes second cooling means for cooling thesulfuric acid solution in any of the above first to third aspects.

The functional solution supply system of a sixth aspect of the presentinvention is characterized in that the use side is a batch typesubstrate cleaning apparatus in any of the above first to fifth aspects.

Effect of the Invention

The functional solution supply system according to the present inventionfor electrolyzing a sulfuric acid solution to prepare a functionalsolution and supplying the functional solution to a use side: comprisesa storage tank for storing the sulfuric acid solution, an electrolyzingapparatus for electrolyzing the sulfuric acid solution, heating meansfor heating the sulfuric acid solution, cooling means for cooling thesulfuric acid solution, and the following circulation lines:

1. a first circulation line for returning the solution discharged fromthe storage tank to the storage tank through the electrolyzing apparatuswithout passing through the heating means;

2. a second circulation line for returning the sulfuric acid solutionintroduced from the use side to the use side through the cooling meansand the storage tank in this order without passing through the heatingmeans; and

3. a third circulation line for returning the sulfuric acid solutionintroduced from the use side to the use side through the heating meanswithout passing through the cooling means and the storage tank.

Thus, by providing the first circulation line, persulfuric acid can bestored in the interior of the storage tank at a high concentration witha small electrolyzing capacity. Moreover, by providing the second andthird circulation lines, the persulfuric acid solution can be heated upin a short time and hence can be supplied as a functional solution ofhigh performance to the use side prior to self-decomposition ofpersulfuric acid.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing a functional solution supply systemaccording to an embodiment of the present invention and functionalsolution supply systems according to modifications thereof.

FIG. 2 is a diagram showing conventional one loop, two loops and threeloops type functional solution supply systems.

EXPLANATION OF REFERENCE NUMERALS

-   -   1 cleaning machine    -   2 storage tank    -   3 electrolytic cell    -   4 cooler    -   5 heater    -   6 cooler    -   7 cooler    -   11 first circulation line    -   12 second circulation line    -   13 third circulation line

BEST MODE FOR CARRYING OUT THE INVENTION

An embodiment of the present invention will be described below on thebasis of FIG. 1( a).

A functional solution supply system of this embodiment includes acleaning machine 1 which is a batch type substrate cleaning apparatus ona use side, a storage tank 2 for storing a sulfuric acid solution, andan electrolytic cell 3 which is an electrolyzing apparatus forelectrolyzing the sulfuric acid solution.

A liquid discharge side of the storage tank 2 and an liquid inlet sideof the electrolytic cell 3 are connected together by a feed line of afirst circulation line 11, while a liquid discharge side of theelectrolytic cell 3 and an liquid inlet side of the storage tank 2 areconnected together by a return line of the first circulation line 11.That is, the storage tank 2 and the electrolytic cell 3 are connectedtogether by the first circulation line 11 to permit circulation of thesulfuric acid solution.

A liquid discharge side of the cleaning machine 1 and an liquid inletside of the storage tank 2 are connected together by a feed line of asecond circulation line 12, while a liquid discharge side of the storagetank 2 and an liquid inlet side of the cleaning machine 1 are connectedtogether by a return line of the second circulation line 12. That is,the cleaning machine 1 and the storage tank 2 are connected together bythe second circulation line 12 to permit circulation of the sulfuricacid solution.

Further, a third circulation line 13 shares a part with the feed line ofthe second circulation line 12 so as to be connected to the liquiddischarge side of the cleaning machine 1 and branches on a downstreamside of the common part. At a position just before the liquid inlet sideof the cleaning machine 1 the third circulation line 13 joins the returnline of the second circulation line 12 so as to be connected to theliquid inlet side of the cleaning machine 1. Thus, the functionalsolution supply system of the present invention is a three loops typesystem different from the conventional art.

On a downstream side of the branched position of the third circulationline 13 and on an upstream side of the position where the secondcirculation line 12 is connected to the liquid inlet side of the storagetank 2, a cooler 4 as cooling means is disposed in the secondcirculation line 12, while on a downstream side of the position wherethe third circulation line 13 branches from the second circulation line12 and at a position before the confluent position where the thirdcirculation line 13 joins the second circulation line 12, a heater 5 asheating means is disposed in the third circulation line 13.

The following description is now provided about the operation of theabove functional solution supply system.

A sulfuric acid solution, which is preferably heated to 40˜80° C., isstored in the storage tank 2. Persulfuric acid is produced byelectrolyzing the sulfuric acid solution while the sulfuric acidsolution is circulated between the storage tank 2 and the electrolyticcell 3 through the first circulation line 11. The persulfuric acid, as asulfuric acid solution containing highly concentrated persulfuric acid,is stored in the storage tank 2. In the present invention, theconstruction of the electrolytic cell is not specially limited, but anelectrolytic cell having a diamond electrode at least as an anode ispreferred.

The highly concentrated persulfuric acid-containing sulfuric acidsolution stored in the storage tank 2 is fed to the cleaning machine 1through the return line of the second circulation line 12. On the otherhand, the sulfuric acid solution which has been used in the cleaningmachine 1 passes through the feed line of the second circulation line 12and is introduced into the storage tank 2 at a relatively small flowrate (at least smaller than the circulation quantity in the firstcirculation line 11) while being cooled to a storage tank temperature(about 40° C.˜80° C.) by the cooler 4. This is to prevent thepersulfuric acid in the storage tank 2 from being diluted with thesulfuric acid solution introduced from the cleaning machine 1. Moreover,since the sulfuric acid solution is cooled by the cooler 4, the solutiontemperature in the storage tank 2 is prevented from rising which wouldexpedite the self-decomposition of persufuric acid. In the presentinvention, the construction of the cooler 4 is not specially limited.There may be used a suitable cooling means such as, for example, a heatexchanger.

On the other hand, the large part of the sulfuric acid solutiondischarged from the cleaning machine 1 is transferred to the thirdcirculation line 13 passing through the feed line of the secondcirculation line 12 on the upstream side and thereafter branching fromit. This sulfuric acid solution is heated by the heater 5. At this time,by setting an outlet temperature of the heater 5 higher than anoperation temperature of the cleaning machine 1, it is possible tocompensate for the quantity of heat required. This high-temperaturesulfuric acid solution and the sulfuric acid solution fed from thestorage tank 2 are fed to the cleaning machine 1, whereby the solutiontemperature in the cleaning machine 1 reaches the operation temperature.Consequently, by joining the second circulation line 12 and the thirdcirculation line 13 just before the liquid inlet side to the cleaningmachine 1 as in this embodiment, the sulfuric acid solution containinghighly concentrated persulfuric acid, which is fed through the secondcirculation line 12, is heated up in an instant and is introduced intothe cleaning machine 1. Persulfuric acid decomposes by itself in a shorttime at a high temperature. Therefore, by heating-up the highlyconcentrated persulfuric acid-containing sulfuric acid solution in aninstant, the heated sulfuric acid solution is introduced into thecleaning machine 1 with almost no room for self-decomposition of thepersulfuric acid. Thus, the persulfuric acid stored in the storage tank2 can be fed to the cleaning machine 1 without waste. In the presentinvention, the construction of the heater 5 is not specially limited.There may be used, for example, the heater or a heat exchanger. In thepresent invention, as described above, the storage tank is used for thepurpose of holding persulfuric acid at a high concentration. Further,the temperature of the functional solution and the persulfuric acidconcentration are adjusted so as to complete cleaning in the cleaningmachine. Therefore, unlike the conventional art, the internaltemperature of the storage tank is maintained at a predetermined lowtemperature.

In the case where the temperature of the cleaning machine 1 is high, forexample, 130° C. or higher, it is presumed that persulfuric acid willdecompose by itself in the interior of the cleaning machine 1, leadingto loss. Actually, however, this is not waste. In order that thepersulfuric acid may act as an oxidizing agent, it is necessary tomaintain the interior of the cleaning machine 1 at a high temperaturefor formation of the sulfuric acid radical, since a sulfuric acidradical produced by the self-decomposition at a high temperature attacksan organic matter. Since the sulfuric acid radical in question isextremely short in life, it is required to be produced in the interiorof the cleaning machine 1 which is the reaction site.

In the system of FIG. 1( a), however, the circulating solution in thefirst circulation line 11 is heated up as a result of heat generation byelectrolysis and returns to the storage tank 2. Therefore, inconsideration of this heated returning solution, it is necessary thatthe temperature of the sulfuric acid solution in the storage tank 2 becontrolled by the cooler 4 disposed ahead of the storage tank 2. Thus,since the load on the cooler 4 has to be higher and the circulationquantity in the second circulation line 12 has to be larger, it isdifficult to control. In this case, it is preferable that a cooler 6 beprovided as second cooling means also behind the storage tank 2 as inthe system of FIG. 1( b). Thus, the cooler 4 can control the temperatureof the solution circulating in the second circulation line 12, while thecooler 6 can control the temperature of the solution circulating in thefirst circulation line 11, each independently, whereby it is possible tolower the load on the cooler 4 and make the amount of the solutioncirculating in the second circulation line 12 small. Without limitationto the system of FIG. 1( b), a cooler 7, for example, as second coolingmeans may perform cooling behind the electrolytic cell as in FIG. 1( c),if the temperature of the solution circulating in the first circulationline can be adjusted.

Although in the present invention the first circulation line isconnected to the storage tank, the configuration is not limited to thedirect return to the storage tank. That is, the first circulation linemay be connected to the second circulation line on the upstream side ofthe storage tank and on the downstream side of the cooler, or the returnline of the second circulation line may be branched (on the upstreamside of the confluent point in case of joining the third circulationline) and used as a feed line of the first circulation line.

Although in the above embodiment the batch type substrate cleaningapparatus was shown as an apparatus to be supplied with the functionalsolution, no limitation is made thereto in the present invention. Thefunctional solution may be supplied to use sides of various applicationscapable of using the electrolyzed sulfuric acid solution and may be usedtherein.

EXAMPLES

The following examples and comparative examples are given to make itclear that the system of the present invention is effective.

Example 1 Three Loops Type

Operation was performed using the system corresponding to FIG. 1( a). Inthe following examples, the first circulation line 11 is designated loop1, the second circulation line 12 is designated loop 2, and the thirdcirculation line 13 is designated loop 3.

(Operating Conditions)

-   -   Wafer: 300 mm dia., Resist thickness=860 nm    -   Cleaning machine 1: Temperature=140° C., Solution capacity=50 L,    -   Number of wafers processed=50 pieces/batch    -   Processing time required: 10 min/batch    -   Cleaning solution: Sulfuric acid concentration=85 wt %    -   Amount of persulfuric acid required in the cleaning machine        1=11.9 g/min.

(Material Balance)

Loop 1: Circulation quantity=8 L/min

-   -   Electrolytic cell 3 inlet temperature=50° C.    -   Electrolytic cell 3 outlet temperature=75° C.

Loop 2: Circulation quantity=6 L/min.

-   -   Cooler 4 outlet temperature=19° C.    -   Storage tank 2 temperature=50° C.    -   Storage tank 2 outlet: Persulfuric acid concentration=2.0 g/L    -   (Persulfuric acid circulation quantity=12.0 g/min)

Loop 3: Circulation quantity=19 L/min

-   -   Heater 5 outlet temperature=174° C.    -   Heater 5 heat load=29.2 kW

That is, by providing the cooler 4, 12.0 g/min of persulfuric acid couldbe fed into the cleaning machine 1 at a circulation flow rate of 6L/min. Moreover, since the temperature of the persulfuric acid solutionjust before introduction is 50° C., self-decomposition scarcely occursand thus there is no waste.

Example 2 Three Loops Type

Operation was performed using the system corresponding to FIG. 1( b).

(Operating Conditions)

-   -   Wafer: 300 mm diameter, Resist thickness=860 nm    -   Cleaning machine 1: Temperature=140° C., Solution capacity=50 L,    -   Number of wafers processed=50 pieces/batch    -   Processing time required=10 min/batch    -   Cleaning solution: Sulfuric acid concentration=85 wt %    -   Amount of persulfuric acid required in the cleaning machine        1=11.9 g/min

(Material Balance)

Loop 1: Circulation quantity=8 L/min

-   -   Electrolytic cell 3 inlet temperature=50° C.    -   Electrolytic cell 3 outlet temperature=75° C.

Loop 2: Circulation quantity=1 L/min

-   -   Cooler 4 outlet temperature=40° C.    -   Storage tank 2 temperature=72° C.    -   Persulfuric acid concentration at storage tank 2 outlet=11.9 g/L    -   (Persulfuric acid circulation quantity=11.9 g/min)

Loop 3: Circulation quantity=24 L/min

-   -   Heater 5 outlet temperature=143° C.    -   Heater 5 heat load=3.8 kW

By providing the cooler 6, 11.9 g/min of persulfuric acid could be fedinto the cleaning machine 1 at a circulation flow rate of 1 L/min. Thatis, by providing the cooler 6, it was possible to lower the load on thecooler 4 and decrease the circulation quantity in the loop 2. Moreover,since the circulation quantity in the loop 2 could be decreased, it waspossible to lower the load on the heater 5. Thus, in this system, thetemperature control became easy and it was possible to suppress the loadon the heater and the load on the cooler.

Comparative Example 1 One Loop Type

Operation was performed using the system corresponding to FIG. 2( a).

(Operating Conditions)

Same as in Example 1. However, the loop number and the loopconfiguration do not always correspond to the examples. (This is alsotrue in the following comparative examples.)

(Material Balance)

Loop 1: Circulation quantity=8 L/min

-   -   Electrolytic cell 23 inlet temperature=50° C.    -   Electrolytic cell 23 outlet temperature=75° C.    -   Persulfuric acid concentration at electrolytic cell 23        outlet=1.49 g/L    -   (Persulfuric acid circulation quantity=11.9 g/min)    -   Heater 25 outlet temperature=140° C.    -   Heater 25 heat load=28.5 kW

That is, for feeding the required amount of persulfuric acid into thecleaning machine 21, the heat load on the heater 25 becomes extremelylarge, which is not practical. Besides, self-decomposition ofpersulfuric acid proceeded because of a long residence time thereof inthe heater 25.

Comparative Example 2 Two Loops Type

Operation was performed using the system corresponding to FIG. 2( b).

(Operating Conditions)

Same as in Example 1.

(Material Balance)

Loop 1 (Circulation path 31 b):

-   -   Circulation quantity=8 L/min    -   Electrolytic cell 23 inlet temperature=50° C.    -   Electrolytic cell 23 outlet temperature=76° C.    -   Persulfuric acid concentration at electrolytic cell 23        outlet=1.49 g/L    -   (Persulfuric acid circulation quantity=11.9 g/min)    -   Cooler 26 outlet temperature=50° C.    -   Storage tank 22 temperature=125° C.

Loop 2 (Circulation path 31 a):

-   -   Circulation quantity=25 L/min    -   Heater 25 outlet temperature=170° C.    -   Heater 25 heat load=20 kW    -   Persulfuric acid concentration at storage tank 22 outlet=0 g/L

That is, although the heat load on the heater 25 became smaller thanthat in Comparative Example 1, it is still excessive and not practical.Moreover, the persulfuric acid concentration at the outlet of thestorage tank 22 became 0 g/L. A circulating solution having apersulfuric acid concentration of 1.49 g/L is supplied from theelectrolytic cell 23 to the storage tank 22, but since the temperatureof the storage tank 22 is adjusted to 125° C., it is presumed that thepersulfuric acid in the storage tank 22 is substantially gone due toself-decomposition thereof.

Comparative Example 3 Two Loops Type

Operation was performed using the system corresponding to FIG. 2( c).

(Operating Conditions)

Same as in Example 1.

(Material Balance)

Loop 1 (Circulation paths 31, 31 b):

-   -   Circulation quantity=8 L/min    -   Electrolytic cell 23 inlet temperature=50° C.    -   Electrolytic cell 23 outlet temperature=76° C.    -   Amount of liquid persulfuric acid at electrolytic cell 23        outlet=1.49 g/L        -   (Persulfuric acid circulation quantity=11.9 g/min)    -   Cooler 26 outlet temperature=50° C.    -   Storage tank 22 temperature=140° C.

Loop 2 (Circulation path 31 a):

-   -   Circulation quantity=17 L/min,    -   Heater 25 outlet temperature=170° C.    -   Heater 25 heat load=26 kW    -   Persulfuric acid concentration at cleaning machine 21 inlet=0.48        g/L

That is, the heat load on the heater 25 scarecely becomes small incomparison with Comparative Example 1 and is still excessive and notpractical.

Comparative Example 4 Three Loops Type

Operation was performed using the system corresponding to FIG. 2( d).

(Operating Conditions)

Same as in Example 1. However, the circulation quantity indicates acirculation quantity at a portion where each loop does not join anyother loop.

(Material Balance)

Loop 1 (Circulation path 31 b):

-   -   Circulation quantity=3.2 L/min    -   Electrolytic cell 23 inlet temperature=50° C.    -   Electrolytic cell 23 outlet temperature=76° C.    -   Persulfuric acid concentration at electrolytic cell 23        outlet=1.49 g/L    -   (Persulfuric acid circulation quantity=4.8 g/min)    -   Storage tank 22 temperature=133° C.

Loop 2 (Circulation path 31):

-   -   Circulation quantity=4.8 L/min    -   Persulfuric acid concentration at cleaning machine 21 inlet=1.49        g/L    -   (Persulfuric acid circulation quantity=7.2 g/min)

Loop 3 (Circulation path 31 a):

-   -   Circulation quantity=21.8 L/min    -   Heater 25 outlet temperature=155° C.    -   Heater 25 heat load=23.4 kW    -   Persulfuric acid concentration at storage tank 22 outlet=0 g/L

That is, although the heat load on the heater 25 becomes a littlesmaller than that in Comparative Example 1, it is still excessive andnot practical. Besides, the persulfuric acid concentration at the outletof the storage tank 22 became 0 g/L. A circulating solution having apersulfuric acid concentration of 1.49 g/L is supplied from theelectrolytic cell 23 to the storage tank 22, but since the temperatureof the storage tank 22 is adjusted to 133° C., it is presumed that thepersulfuric acid in the storage tank 22 is substantially gone due toself-decomposition thereof.

1. A functional solution supply system for electrolyzing a sulfuric acidsolution to prepare a functional solution and supplying the functionalsolution to a use side, the system comprising a storage tank for storingthe sulfuric acid solution, an electrolyzing apparatus for electrolyzingthe sulfuric acid solution, heating means for heating the sulfuric acidsolution, cooling means for cooling the sulfuric acid solution, andincluding the following three circulation lines:
 1. a first circulationline for returning the sulfuric acid solution discharged from thestorage tank to the storage tank through the electrolyzing apparatuswithout passing through the heating means;
 2. a second circulation linefor returning the sulfuric acid solution introduced from the use side tothe use side through the cooling means and the storage tank in thisorder without passing through the heating means; and
 3. a thirdcirculation line for returning the sulfuric acid solution introducedfrom the use side to the use side through the heating means withoutpassing through the cooling means and the storage tank.
 2. Thefunctional solution supply system according to claim 1, wherein thesecond circulation line and the third circulation line join just beforethe return to the use side.
 3. The functional solution supply systemaccording to claim 1, wherein the second circulation line and the thirdcirculation line are branched after being introduced from the use side.4. The functional solution supply system according to claim 1, whereinon a downstream side of the storage tank and on an upstream side of theelectrolyzing apparatus the first circulation line includes secondcooling means for cooling the sulfuric acid solution.
 5. The functionalsolution supply system according to claim 1, wherein on a downstreamside of the electrolyzing apparatus and on an upstream side of thestorage tank the first circulation line includes second cooling meansfor cooling the sulfuric acid solution.
 6. The functional solutionsupply system according to claim 1, wherein the use side is a batch typesubstrate cleaning apparatus.
 7. A functional solution supply method forelectrolyzing a sulfuric acid solution to prepare a functional solutionand supplying the functional solution to a use side, comprising: acirculation step of discharging a sulfuric acid solution from a storagetank for storing the sulfuric acid solution, electrolyzing the sulfuricacid solution without being passed through heating by heating means, andreturning the sulfuric acid solution after the electrolysis to thestorage tank; a circulation step of cooling the sulfuric acid solutionintroduced from the use side, by cooling means, without being passedthrough the heating by the heating means, feeding the sulfuric acidsolution after the cooling to the storage tank, discharging the sulfuricacid solution from the storage tank and returning it to the use side;and a circulation step of heating the sulfuric acid solution introducedfrom the use side, by the heating means, without being passed throughthe cooling by the cooling means and without being passed through thestorage tank, and returning the heated sulfuric acid solution to the useside.
 8. The functional solution supply method according to claim 7,wherein in the circulation step of returning the sulfuric acid solutionintroduced from the use side to the use side from the storage tank andthe circulation step of returning the sulfuric acid solution introducedfrom the use side to the use side without being passed through thestorage tank, the sulfuric acid solution not having been passed throughthe heating and the sulfuric acid solution haying been passed throughthe heating are joined just before the return to the use side and arereturned in the joined state to the use side.
 9. The functional solutionsupply system according to claim 2, wherein the second circulation lineand the third circulation line are branched after being introduced fromthe use side.
 10. The functional solution supply system according toclaim 2, wherein on a downstream side of the storage tank and on anupstream side of the electrolyzing apparatus the first circulation lineincludes second cooling means for cooling the sulfuric acid solution.11. The functional solution supply system according to claim 3, whereinon a downstream side of the storage tank and on an upstream side of theelectrolyzing apparatus the first circulation line includes secondcooling means for cooling the sulfuric acid solution.
 12. The functionalsolution supply system according to claim 2, wherein on a downstreamside of the electrolyzing apparatus and on an upstream side of thestorage tank the first circulation line includes second cooling meansfor cooling the sulfuric acid solution.
 13. The functional solutionsupply system according to claim 3, wherein on a downstream side of theelectrolyzing apparatus and on an upstream side of the storage tank thefirst circulation line includes second cooling means for cooling thesulfuric acid solution.
 14. The functional solution supply systemaccording to claim 2, wherein the use side is a batch type substratecleaning apparatus.
 15. The functional solution supply system accordingto claim 3, wherein the use side is a batch type substrate cleaningapparatus.
 16. The functional solution supply system according to claim4, wherein the use side is a batch type substrate cleaning apparatus.17. The functional solution supply system according to claim 5, whereinthe use side is a batch type substrate cleaning apparatus.